CN101627009B - Process and plant for the production of an aqueous solution comprising urea - Google Patents
Process and plant for the production of an aqueous solution comprising urea Download PDFInfo
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- CN101627009B CN101627009B CN2008800039127A CN200880003912A CN101627009B CN 101627009 B CN101627009 B CN 101627009B CN 2008800039127 A CN2008800039127 A CN 2008800039127A CN 200880003912 A CN200880003912 A CN 200880003912A CN 101627009 B CN101627009 B CN 101627009B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
- C07C273/14—Separation; Purification; Stabilisation; Use of additives
- C07C273/16—Separation; Purification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/206—Ammonium compounds
- B01D2251/2062—Ammonia
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00018—Construction aspects
- B01J2219/00024—Revamping, retrofitting or modernisation of existing plants
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
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Abstract
The present invention regards a process for the production of an aqueous solution comprising urea for use in the removal of nitrogen oxides from combustion gas or fumes, the process being characterised in that it comprises the steps of: - subjecting at least a part of a urea-concentrated aqueous solution comprising residual free ammonia, obtained directly from or downstream of a recovery section of a plant for the production of urea, to washing with carbon dioxide, so obtaining a first vapour phase comprising carbon dioxide and optionally ammonia and a urea-concentrated aqueous solution comprising carbamate and essentially lacking in free ammonia, and - diluting said urea-concentrated aqueous solution comprising carbamate and essentially lacking in free ammonia with water until the desired concentration of urea in aqueous solution is reached.
Description
Technical field
Aspect the most widely, the present invention relates to the method that a kind of preparation contains the aqueous solution of urea, by the reduction reaction of oxynitride and gaseous ammonia, this aqueous solution intends being used for removing the oxynitride (NOx) that is present in combustion exhaust.
Concrete, what the present invention relates to aforementioned type is the synthetic method for preparing urea of raw material with ammonia and carbonic acid gas.
The preparation that the invention still further relates to the method for implementing aforementioned type contains the equipment of the aqueous solution of urea.
Background technology
As everyone knows, the international law of the gaseous effluent (burning gas or waste gas) that produces about the burning of fossil oil, in more and more stricter mode, force significantly to reduce the pollutent that is included in the described gaseous effluent, oxynitride (NOx) particularly wherein is because oxynitride (NOx) is the origin cause of formation of described acid rain.
For this purpose, developed the method for the gaseous effluent of different processing fossil-fueleds, especially, the method for selective catalyst reduction of nitrogen oxides (NOx)---more is called the SCR method with being widely known by the people---and is widely used, and it can remove most of NO and NO in the gaseous effluent
2, be translated into to environment inert compound, as nitrogen and water vapour.
This method is specially adapted to reduce in a large number heavy-duty car, particularly has the oxynitride of gaseous effluent of the heavy-duty car of diesel oil or turbo-charging diesel motor.
The SCR method is based on following series of chemical, and ammonia and oxygen by in the air-flow of needs purification with reaction of nitrogen oxides, cause the removal oxynitride:
4NO+O
2+4NH
3＝4N
2+6H
2O
6NO
2+8NH
3＝7N
2+12H
2O
NO+NO
2+2NH
3＝2N
2+3H
2O
More than shown in reaction be strong exothermal reaction, according to estimates, contain the air-flow of 1000ppm NOx, in conversion process, its temperature-averaging raises 10～11 ℃.
The preferred temperature range of SCR method is 180 ℃～350 ℃, transforms under 180 ℃ the temperature not exclusively being lower than, and therefore can not guarantee required clearance usually; And in the temperature that is higher than 350 ℃, side reaction can take place in ammonia in the air-flow and oxygen, as at 400 ℃, mainly by following reaction, loses about 5～10% ammonia.
4NH
3+5O
2＝4NO+6H
2O (4)
The appearance of this reaction will resist the reaction that takes place at the scavenging process that is higher than under 350 ℃ the temperature, and the actual demand that is not less than 200 ℃ of minimum operating temperatures need be adopted suitable catalysis system or not rely on the catalyzer of process operation; State-of-the art heavy-duty car as being equipped with the heavy-duty car of Euro 4 or Euro 5 engines, all is equipped with this catalysis system or catalyzer usually.
For the adding of the required ammonia of operation SCR method, all use ammonia or urea in the aqueous solution as everyone knows, its concentration is generally the 15-35% of aqueous solution weight.
This aqueous solution is injected into by atomizing nozzle in SCR catalysis system (or catalyzer) gas stream upstream that needs to purify, and the upstream of catalysis system also can be another kind of fixedly mixing device, with the required turbulent flow of assurance air-flow, and disperses reactant smoothly.
Especially, in said process owing to will avoid the transportation of the ammonia or the ammonia aqueous solution or the hazard of storage, with the urea in the aqueous solution as reactant right and wrong usefulness usually.In this case, according to following reaction, obtain the required ammonia of purification of air-flow to be processed from the decomposition in situ of urea.
N
2H
4CO+H
2O＝2NH
3+CO
2
Decomposition reaction is thermo-negative reaction, and the air-flow that institute's heat requirement is handled by need (generally all have and be higher than 300 ℃ temperature) provides, and this also can be reduced to the temperature of gas the preferred value of the SCR method shown in above.
For the urea that obtains to be used for to remove the aqueous solution of oxynitride, prior art estimates that at first dilute with water urea obtains required urea concentration up to obtained aqueous solution then by conventional urea equipment synthetic preparation molten or granular urea.
Adopt this method, owing to can obtain the urea synthesis (molten or particulate state) of high purity (99% or higher purity), just may obtain very pure and do not have the finished product (urea in the aqueous solution) of free ammonia (because niff and to the influence of environment does not wish to have ammonia).
Yet, because in order to remove ammonia by obtaining high-purity fusion or granular urea, need to concentrate the synthetic aqueous solution of urea that obtains, to remove solvent (water) wherein fully, and described solvent is introduced again at the dissolving step of fusion or granular urea subsequently, therefore aforesaid method comprises a large amount of energy consumptions, and a kind of preparation method of urea-containing water vapour is existing disclosed in as WO2006/096048.
Summary of the invention
Therefore, the technical problem that the present invention is implied is invention and implements the method that a kind of preparation is used to remove the aqueous solution that contains urea of burning gas or nitrogen oxides from exhaust gas, the raw material of this aqueous solution is the aqueous solution of urea synthesis, this method has overcome the shortcoming of above-mentioned prior art, particularly, compare with currently known methods, the method for the above-mentioned type can be removed the ammonia in the urea synthesis aqueous solution substantially under lower energy expenditure.
Can be according to the present invention, be used to remove the method for the aqueous solution that contains urea of burning gas or nitrogen oxides from exhaust gas by preparation, solve this technical problem, its characteristics are said method comprising the steps of:
-at least a portion is contained the concentrating urea aqueous solution (urea-concentrated aqueous solution) of residual free ammonia, it is directly from the recovery zone of urea production equipment or the downstream of recovery zone, wash with carbonic acid gas, contain carbonic acid gas and may contain first vapor phase of ammonia obtaining, and to contain carbaminate and be substantially devoid of the concentrating urea aqueous solution of free ammonia;
The described concentrating urea aqueous solution that contains carbaminate and be substantially devoid of free ammonia of-dilute with water reaches required urea concentration in the aqueous solution.
Preferably, the required urea concentration in the described aqueous solution is the 15-35% weight of solution weight.
The particularly preferred embodiment according to the present invention contains the concentrating urea aqueous solution of residual free ammonia, and its at least a portion is washed by carbonic acid gas, is directly to obtain from the recovery zone of urea equipment.
Term " urea recovery zone " is meant and comprises the aqueous solution of urea that is used to handle synthetic acquisition, with this part of the urea equipment of the conventional equipment of the content that reduces carbaminate in this solution and free ammonia, this device comprises a heat operation at least or preferably carries dissociator or the gas stripping column that the agent mode is moved with gas.In addition, the pressure of recovery zone is lower than the synthetic district for preparing urea with ammonia and carbonic acid gas usually.
According to another preferred implementation of the present invention, contain the concentrating urea aqueous solution of residual free ammonia, its at least a portion is washed by carbonic acid gas, is the evaporating area (evaporation section) from the downstream, described recovery zone that is arranged at urea equipment.
For this purpose, contain the concentrating urea aqueous solution of residual free ammonia, its at least a portion is washed by carbonic acid gas, preferably obtains from the vaporizer that is used for concentrating from the described evaporating area of the concentrating urea solution that contains residual free ammonia of urea equipment recovery zone.
Because the present invention, directly from the downstream of the recovery zone of urea production equipment or recovery zone, at least a portion still contains the concentrating urea aqueous solution of residual free ammonia, and advantageously with the carbonic acid gas washing, rather than the above-mentioned known mode of picture is through pervaporation.
Compared with prior art, this has brought considerable advantage, comprises and required the comparing of evaporation, needs less energy expenditure with the carbonic acid gas washing, thereby reduces energy expenditure greatly.
In addition, will advantageously remove a large amount of free ammonia that contains in the described solution, be translated into harmless carbaminate (from the angle of environmental influence), and may carry by the gas of carbonic acid gas and movable its part being sent in the gas phase with carbonic acid gas washing.
Therefore, the concentrating urea aqueous solution through the carbonic acid gas washing is substantially free of free ammonia, be diluted with water to that urea in the aqueous solution has proper concn (the 15-35% weight percent of aqueous solution weight) and content is the following ammonia of sense of smell value (olfactory values), preferably less than 150ppm, it can be advantageously used in removes burning gas or nitrogen oxides from exhaust gas.
Be noted that more the ammonium carbamate in the above-mentioned aqueous solution of urea can decompose with urea in the NOx process in using described solution removal burning gas, so newly-generated carbonic acid gas and ammonia, the latter can be used for removing NOx.
Above-mentioned technical problem also can solve by implementing the equipment that method for preparing of the present invention contains the aqueous solution of urea, and this aqueous solution is used to remove burning gas or nitrogen oxides from exhaust gas.
According to the embodiment of the present invention, described equipment comprises urea synthesis district and the urea recovery zone that mutual fluid is communicated with, and its characteristics are also to comprise:
-washing section adopts the carbonic acid gas washing, is arranged at the downstream of described urea recovery zone;
-feed-pipe is arranged between described urea recovery zone and the described washing section, so that at least a portion is added described washing section from the described urea recovery zone concentrating urea aqueous solution that obtain, that contain residual free ammonia;
-feed carbon dioxide pipe adds described washing section with carbonic acid gas;
-vent pipe is used to eject from described washing section, contains carbaminate and do not contain the concentrating urea aqueous solution of free ammonia substantially; And
-filler pipe is communicated with described vent pipe fluid from washing section, to dilute the described concentrating urea aqueous solution that contains carbaminate and do not contain free ammonia substantially, obtains required urea concentration until the aqueous solution.
According to another embodiment of the present invention, this equipment comprises the urea synthesis district, urea recovery zone and the evaporating area that comprises first vaporizer and second vaporizer, and the mutual fluid in described district is communicated with, and the characteristics of this equipment are, also comprise:
-washing section adopts the carbonic acid gas washing, is arranged at the downstream of described urea recovery zone;
-feed-pipe is arranged between described first vaporizer and the described washing section, so that at least a portion is added described washing section from described first vaporizer concentrating urea aqueous solution that obtain, that contain residual free ammonia;
-feed-pipe adds described washing section with carbonic acid gas;
-vent pipe is used to eject from described washing section, contains carbaminate and do not contain the concentrating urea aqueous solution of free ammonia substantially; And
-filler pipe is communicated with described vent pipe fluid from washing section, to dilute the described concentrating urea aqueous solution that contains carbaminate and do not contain free ammonia substantially, obtains required urea concentration in the aqueous solution.
According to the present invention, preparation contains equipment (ex-novo) design or the manufacturing again of the aqueous solution of urea, or preferably transforms the existing installation of preparation urea synthesis.
Under latter event, according to a further aspect in the invention, improving one's methods, (transformation) to can be used for ammonia and carbonic acid gas be the existing installation of the type of feedstock production urea, it comprises urea synthesis district and urea recovery zone that fluid is communicated with, its characteristics are that this improves one's methods further comprising the steps of:
-washing section that adopts the carbonic acid gas washing is set in the downstream of described urea recovery zone;
-between described urea recovery zone and described washing section, feed-pipe is set, so that the concentrating urea aqueous solution that contains residual free ammonia that at least a portion is discharged by described urea recovery zone adds described washing section;
-the feed carbon dioxide pipe that carbonic acid gas is added described washing section is set;
-be provided for ejecting from described washing section, contain carbaminate and do not contain the vent pipe of the concentrating urea aqueous solution of free ammonia substantially; And
-filler pipe that is communicated with described vent pipe fluid from washing section is set, to dilute the described concentrating urea aqueous solution that contains carbaminate and do not contain free ammonia substantially, the required urea concentration of acquisition in the aqueous solution.
According to another embodiment of the present invention, improving one's methods, (transformation) to can be used for ammonia and carbonic acid gas be the existing installation of the type of feedstock production urea, it comprises urea synthesis district, urea recovery zone and comprises first vaporizer and the evaporating area of second vaporizer, the mutual fluid in described district is communicated with, its characteristics are that this improves one's methods further comprising the steps of:
-washing section that adopts the carbonic acid gas washing is set in the downstream of described urea recovery zone;
-between described first vaporizer and described washing section, feed-pipe is set, so that at least a portion is added described washing section from described first vaporizer concentrating urea aqueous solution that obtain, that contain residual free ammonia;
-the feed carbon dioxide pipe that carbonic acid gas is added described washing section is set;
-be provided for ejecting from described washing section, contain carbaminate and do not contain the vent pipe of the concentrating urea aqueous solution of free ammonia substantially; And
-set in advance the filler pipe that is communicated with described vent pipe fluid from washing section, to dilute the described concentrating urea aqueous solution that contains carbaminate and do not contain free ammonia substantially, in the aqueous solution, obtain required urea concentration.
According to the present invention, preparing the more characteristics of method of aqueous solution of urea and advantage will more clearly describe in preferred embodiment with reference to the accompanying drawings following, but it is used for explanation and is not used in restriction.
Description of drawings
Fig. 1 is according to prior art, and preparation is used to remove the structure iron of equipment of the aqueous solution that contains urea of burning gas or nitrogen oxides from exhaust gas.
Fig. 2 is according to the present invention, and preparation is used to remove the structure iron of equipment of the aqueous solution that contains urea of burning gas or nitrogen oxides from exhaust gas.
Embodiment
Referring to Fig. 1, according to prior art, preparation is used for removing the integral body of equipment of the aqueous solution that contains urea of oxynitride of combustion exhaust with numeral 1 expression.
In equipment 1, the method for preparing aqueous solution of urea is based on the urea synthesis of preparation molten, dilute with water fusing urea then, required urea concentration in obtaining the aqueous solution.
More particularly, equipment 1 is included in the urea synthesis district 2 of preset high-pressure (for example 135-175 crust) operation, in the urea recovery zone 3 of default low pressure (for example 1-10 crust) operation, evaporating area 4, and the processing/enrichment region 5 of the gas phase that obtains of self-evaporatint n. district 4, describedly respectively distinguish mutual fluid and be communicated with.
Equipment 1 also comprises the pipeline 6 and 7 that adds required carbonic acid gas of urea synthesis and the extremely synthetic district 2 of ammonia respectively.In district 2, carbonic acid gas and ammonia are reacted in suitable reactor, make the aqueous solution that contains urea, ammonium carbamate and free ammonia, it adds in the urea recovery zone 3 by pipeline 8.
In urea recovery zone 3, the aforementioned aqueous solution that contains urea, ammonium carbamate and free ammonia is at suitable, this device as routine, as carrying out the disaggregating treatment of carbaminate in stripping tower, the dissociator etc., to obtain to contain the gas phase of ammonia and carbonic acid gas, contain residual free ammonia concentrating urea solution (for example urea concentration be solution weight 70%).
3 gas phases that contain ammonia and carbonic acid gas of discharging from the urea recovery zone, be suitably recycled to synthetic district 2 by pipeline 9, further being converted into urea, and from the urea recovery zone 3 concentrating urea solutions that contain residual free ammonia of discharging, add evaporating area 4 by pipeline 10.
More particularly, the aforementioned gas phase that contains ammonia and carbonic acid gas is preferably in the mode (to comprise the solution form of ammonium carbamate) of condensation, in the condenser of basis as routine of urea recovery zone 3, be recycled to synthetic district by condensed fluid (carbamate solution normally circulates).
The air-flow that comprises rare gas element (for example nitrogen, hydrogen, oxygen etc.), it appears at usually, and the synthetic district 2 with guard reactor avoids corrosion in the carbon dioxide, also discharges from urea recovery zone 3 by pipeline 11.
In evaporating area 4, the aforementioned concentrating urea solution that comprises residual free ammonia as one or more vaporizers, carries out the evaporation of solvent (water), and removes residual free ammonia by conventional device itself, obtains fusing urea and the gas phase that contains water and ammonia.
Self-evaporatint n. district 4 gas phases that discharge, that contain water and ammonia suitably add treatment zone 5 by pipeline 12, and it comprises a series of conventional equipments with condensation, and isolates residual gas phase component (mainly being ammonia and carbonic acid gas) from water.
In the exit of treatment zone 5, the liquid that also obtains to be made up of water basically by pipeline 13 flows, with further utilization; Also obtain the main air-flow of being made up of ammonia and carbonic acid gas by pipeline 15, it is recycled to urea recovery zone 3.
In urea recovery zone 3, the aforementioned air-flow process conventional processing of mainly forming by ammonia and carbonic acid gas, and preferably be circulated to synthetic district 2 with the condensation form.
In addition, self-evaporatint n./disassociation district 4 obtains, by the fusing urea of pipeline 16 by district's 4 discharges, with at pipeline 17, it is communicated with vent pipe 16 fluids of fusing urea, the water of middle circulation mixes, thereby obtains having the aqueous solution of urea of required urea concentration, is 32% weight concentration of solution weight as concentration.
Fig. 2 represents the equipment of aqueous solution of urea produced according to the present invention, and this aqueous solution is used for removing the oxynitride of combustion exhaust, and equipment integral is with numeral 20 expressions.
More particularly, equipment 20 according to the present invention can prepare urea synthesis and be used for removing the aqueous solution of urea of the oxynitride of combustion exhaust, with detailed in this manual explanation.
The same numeral of equipment 20 be meant with aforesaid device 1 structure on or identical corresponding component on the function, for for the purpose of concise and to the point, this kind parts will be not described in detail in addition.
As above-mentioned equipment 1, equipment 20 is included in the urea synthesis district 2 of preset high-pressure (for example 135-175 crust) operation, in the urea recovery zone 3 of default low pressure (for example 1-10 crust) operation, evaporating area 4, and the processing/enrichment region 5 of the gas phase that obtains of self-evaporatint n. district 4, describedly respectively distinguish mutual fluid and be communicated with.
More particularly, in the present embodiment, evaporating area 4 comprises the first vaporizer 4a and the second vaporizer 4b that order is provided with, and its mutual fluid is communicated with and is communicated with urea recovery zone 3 (by the first vaporizer 4a) fluid.
According to the present invention, equipment 20 also comprises and is arranged at 3 downstreams, urea recovery zone, adopt the washing section 22 of carbonic acid gas, and be arranged on pipeline 23 between urea recovery zone 3 and the washing section 22, with will be from urea recovery zone 3, retain a part of concentrating urea aqueous solution of residual free ammonia, join in the described washing section 22.
More particularly, pipeline 23 with from urea recovery zone 3, described vent pipe 10 fluids that contain the concentrating urea aqueous solution of residual free ammonia are communicated with, by this pipeline, the remaining concentrating urea aqueous solution that contains residual free ammonia joins evaporating area 4.
At washing section 22, adopt by suitable pipeline 24, join the aforementioned concentrating urea aqueous solution that contains residual free ammonia of carbonic acid gas washing of washing section 22, it mainly is converted into carbaminate with the residual free ammonia in the described solution, and the gas of the carbon dioxide gas stream by adding washing section 22 is proposed activity and may be removed part ammonia in the gas phase.
For this purpose, washing section 22 comprises one or more conventional equipments that carry out exchange of substance between liquid and gas, as gas purifier particularly, and board-like distillation column etc.
Therefore in the outlet of washing section 22, the concentrating urea aqueous solution that obtains containing carbaminate He be substantially devoid of free ammonia, and contain carbonic acid gas and may contain the gas phase of ammonia.
According to the present invention, contain carbaminate and be substantially devoid of the concentrating urea aqueous solution of free ammonia from what washing section 22 obtained, be used in the water dilution of circulation in the pipeline 17, pipeline 17 is communicated with described vent pipe 25 fluids from washing section 22, obtaining having required urea concentration in the aqueous solution, is 30% weight concentration of solution weight as concentration.
And will add urea recovery zone 3 with the gas phase that may contain ammonia from the carbonic acid gas that contains that washing section 22 is discharged, further to carry out basis as processed conventionally processing, as by being arranged on washing section 22 and urea recovery zone 3 intermediary pipelines 27, make it preferably to be suitably recycled in the synthetic district 2 with condensing mode.
Should be noted that advantageously the carbonic acid gas purgative gas that adds washing section 22 can be the part of the carbon dioxide that provides for urea synthesis district 2.Optionally, carbonic acid gas also can be from external source.Preferably, the carbonic acid gas purgative gas of adding washing section 22 is in excess in the ammonia in the concentrating urea solution, so that described ammonia is converted into carbaminate in quantized mode (in a quantitative way) basically.
More should note, according to the present invention, in the concentrating urea aqueous solution that contains residual free ammonia that discharge urea recovery zone 3, do not send into the remainder of washing section 22, the first vaporizer 4a that advantageously adds evaporating area by pipeline 10, by connecting tube 31, enter the second vaporizer 4b then from the first vaporizer 4a.Can still be contained residual free ammonia, more spissated aqueous solution of urea from the first vaporizer 4a, and in the second vaporizer 4b, solvent is removed fully, thereby obtained the fusing urea by pipeline 16 discharges from the second vaporizer 4b.From vaporizer 4a and 4b, can obtain containing the gas phase of water and ammonia respectively, it is admitted to aforesaid district 5 and handles respectively by pipeline 12a and 12b.
(not to illustrate) according to one embodiment of present invention can reckon with all concentrating urea aqueous solution that contains residual free ammonia is sent into the washing section 22 that adopts carbonic acid gas, obtains to be used to remove the aqueous solution that NOx contains urea so that only produce.In the case, just do not need evaporating area 4 and treatment zone 5, perhaps as have these districts (for example under the situation of transforming urea equipment), just pass into disuse.
(shown in Fig. 2 dotted line) according to another embodiment of the invention can reckon with by first vaporizer 4a partial concentration aqueous solution of urea that discharge, that contain residual free ammonia, by connecting tube 30, sends into washing section 22.This mode can be used as possibility, and the concentrating urea aqueous solution that contains residual free ammonia that recovery zone 3 is discharged adds washing section 22 or other similar supply.
Therefore method and apparatus according to the invention has purposes quite flexibly, because they make it become possibility: for satisfying specific and accidental needs, can be at the point different and that add of equipment, the aqueous solution that will contain urea and residual free ammonia is sent to washing.
Another advantage of the present invention is in fact, under the situation of transforming existing installation, owing to only need set in advance washing section simply, and should district and the urea recovery zone of existing installation or the suitable connecting tube between the evaporating area, the change that need carry out seldom and need not a large amount of investments.
Certainly; in order to satisfy specific and accidental needs; those skilled in the art can make a large amount of modifications and change to above-described method and apparatus, contains the aqueous solution of urea with preparation, and these are included in protection scope of the present invention that following claim limits.
Claims (18)
1. a method for preparing the aqueous solution that contains urea that is used to remove burning gas or nitrogen oxides from exhaust gas is characterized in that, may further comprise the steps:
-at least a portion is contained the concentrating urea aqueous solution of residual free ammonia, it is directly from the recovery zone of urea production equipment or the downstream of recovery zone, wash with carbonic acid gas, obtaining containing first gas phase of carbonic acid gas, and contain carbaminate and be substantially devoid of the concentrating urea aqueous solution of free ammonia; And
The described concentrating urea aqueous solution that contains carbaminate and be substantially devoid of free ammonia of-dilute with water reaches required urea concentration up to the aqueous solution.
2. the method for claim 1 is characterized in that, the described concentrating urea aqueous solution that contains residual free ammonia, and its at least a portion is washed by carbonic acid gas, is that direct urea recovery zone (3) from urea equipment obtains.
3. the method for claim 1 is characterized in that, the described concentrating urea aqueous solution that contains residual free ammonia, and its at least a portion is washed by carbonic acid gas, from the evaporating area (4) in the downstream, described recovery zone (3) that is arranged at urea equipment.
4. method as claimed in claim 3, it is characterized in that, the described concentrating urea aqueous solution that contains residual free ammonia, its at least a portion is washed by carbonic acid gas, from being used for concentrating vaporizer (4a) acquisition from the described evaporating area of the concentrating urea aqueous solution of the described recovery zone (3) of urea equipment.
5. as the described method of above-mentioned arbitrary claim, it is characterized in that, with the described concentrating urea aqueous solution dilute with water that contains carbaminate and be substantially devoid of free ammonia, the required urea concentration in this aqueous solution is based on the 15-35% of aqueous solution weight.
6. the method for claim 1, it is characterized in that, described method is further comprising the steps of, the aqueous solution that contains urea, ammonium carbamate and free ammonia that will obtain from the synthetic district (2) of urea equipment, exist in described urea recovery zone (3) or when not existing gas to propose agent, decompose ammonium carbamate, obtaining to contain second gas phase of ammonia and carbonic acid gas, and the described concentrating urea aqueous solution that contains residual free ammonia.
7. as the described method of above-mentioned claim 1, it is characterized in that described method also comprises the step that described first gas phase that contains carbonic acid gas and may contain ammonia is added described urea recovery zone (3).
8. method as claimed in claim 6 is characterized in that, described method also comprises described second gas phase that contains ammonia and carbonic acid gas and to be recycled to the step of urea synthesis district (2) with the condensation form.
9. as the described method of above-mentioned claim 1, it is characterized in that described method also comprises evaporates in described evaporating area (4) not through the concentrating urea aqueous solution part that contains residual free ammonia of carbonic acid gas washing described, to obtain fusing urea.
10. equipment for preparing the aqueous solution that contains urea that is used to remove burning gas or nitrogen oxides from exhaust gas, described equipment comprises urea synthesis district (2) and urea recovery zone (3) that mutual fluid is communicated with, and it is characterized in that also comprising:
-washing section (22) adopts the carbonic acid gas washing, is arranged at the downstream of described urea recovery zone;
-feed-pipe (23) is arranged between described urea recovery zone (3) and the described washing section (22), so that at least a portion is added described washing section (22) from described urea recovery zone (3) the concentrating urea aqueous solution that obtain, that contain residual free ammonia;
-feed carbon dioxide pipe (24) adds described washing section (22) with carbonic acid gas;
-vent pipe (25) is used to eject from described washing section (22), contains carbaminate and do not contain the concentrating urea aqueous solution of free ammonia substantially; And
-filler pipe (17) is communicated with described vent pipe (25) fluid from washing section (22), to dilute the described concentrating urea aqueous solution that contains carbaminate and do not contain free ammonia substantially, obtains required urea concentration in the aqueous solution.
11. equipment for preparing the aqueous solution that contains urea that is used to remove burning gas or nitrogen oxides from exhaust gas, described equipment comprises urea synthesis district (2), urea recovery zone (3) and comprises first vaporizer (4a) and the evaporating area (4) of second vaporizer (4b), described urea synthesis district (2), urea recovery zone (3) and evaporating area (4) fluid mutually are communicated with, it is characterized in that described equipment also comprises:
-washing section (22) adopts the carbonic acid gas washing, is arranged at the downstream of described urea recovery zone (3);
-feed-pipe (30) is arranged between described first vaporizer (4a) and the described washing section (22), so that at least a portion is added described washing section (22) from described first vaporizer (4a) the concentrating urea aqueous solution that obtain, that contain residual free ammonia;
-feed carbon dioxide pipe (24) adds described washing section (22) with carbonic acid gas;
-vent pipe (25) is used to eject from described washing section (22), contains carbaminate and do not contain the concentrating urea aqueous solution of free ammonia substantially; And
-filler pipe (17) is communicated with described vent pipe (25) fluid from washing section (22), to dilute the described concentrating urea aqueous solution that contains carbaminate and do not contain free ammonia substantially, obtains required urea concentration in the aqueous solution.
12. as claim 10 or 11 described equipment, it is characterized in that, described equipment also is included in the pipeline (27) between described washing section (22) and the described urea recovery zone (3), adding described urea recovery zone (3) with the gas phase that may contain ammonia from the carbonic acid gas that contains that described washing section (22) is discharged.
13. equipment as claimed in claim 10 is characterized in that, described equipment also comprises:
-evaporating area (4) is arranged on the downstream of described urea recovery zone (3);
-pipe connecting (10) is arranged between urea recovery zone (3) and the described evaporating area (4), adds described evaporating area (4) with the described concentrating urea aqueous solution that at least a portion is obtained from described urea recovery zone (3), contain residual free ammonia;
-vent pipe (16) is from the urea synthesis of described evaporating area (4) discharge molten.
14. equipment as claimed in claim 12 is characterized in that, described equipment also comprises:
-evaporating area (4) is arranged on the downstream of described urea recovery zone (3);
-pipe connecting (10) is arranged between urea recovery zone (3) and the described evaporating area (4), adds described evaporating area (4) with the described concentrating urea aqueous solution that at least a portion is obtained from described urea recovery zone (3), contain residual free ammonia;
-vent pipe (16) is from the urea synthesis of described evaporating area (4) discharge molten.
15. equipment as claimed in claim 11 is characterized in that, described equipment also comprises:
-pipe connecting (10), be arranged between described first vaporizer (4a) of urea recovery zone (3) and evaporating area (4), add described first vaporizer (4a) with the described concentrating urea aqueous solution that will obtain from described urea recovery zone (3), contain residual free ammonia;
-pipe connecting (31), be arranged between first vaporizer (4a) and second vaporizer (4b) of described evaporating area (4), add second vaporizer (4b) with the described concentrating urea aqueous solution that at least a portion is obtained from described first vaporizer (4a), contain residual free ammonia;
-vent pipe (16) is from the urea synthesis of second vaporizer (4b) discharge molten.
16. one kind what comprise urea synthesis district (2) that mutual fluid is communicated with and urea recovery zone (3) is the improving one's methods of existing installation of the type of feedstock production urea with ammonia and carbonic acid gas, it is characterized in that, further comprising the steps of:
-washing section (22) that adopts the carbonic acid gas washing is set in the downstream of described urea recovery zone (3);
-between described urea recovery zone (3) and described washing section (22), feed-pipe (23) is set, so that the concentrating urea aqueous solution that contains residual free ammonia that at least a portion is discharged by described urea recovery zone (3) adds described washing section (22);
-the feed carbon dioxide pipe (24) that carbonic acid gas is added described washing section (22) is set;
-be provided for ejecting from described washing section (22), contain carbaminate and do not contain the vent pipe (25) of the concentrating urea aqueous solution of free ammonia substantially; And
-filler pipe (17) that is communicated with described vent pipe (25) fluid from washing section (22) is set, to dilute the described concentrating urea aqueous solution that contains carbaminate and do not contain free ammonia substantially, the required urea concentration of acquisition in the aqueous solution.
17. one kind comprise urea synthesis district (2), urea recovery zone (3) and comprise first vaporizer (4a) and the evaporating area (4) of second vaporizer (4b) be the improving one's methods of existing installation of the type of feedstock production urea with ammonia and carbonic acid gas, described urea synthesis district (2), urea recovery zone (3), and evaporating area (4) fluid connection mutually, it is characterized in that, described improve one's methods further comprising the steps of:
-washing section (22) that adopts the carbonic acid gas washing is set in the downstream of described urea recovery zone (3);
-between described first vaporizer (4a) and described washing section (22), feed-pipe (30) is set, so that at least a portion is added described washing section (22) from described first vaporizer (4a) the concentrating urea aqueous solution that obtain, that contain residual free ammonia;
-the feed carbon dioxide pipe (24) that carbonic acid gas is added described washing section (22) is set;
-be provided for ejecting from described washing section (22), contain carbaminate and do not contain the vent pipe (25) of the concentrating urea aqueous solution of free ammonia substantially; And
-filler pipe (17) that is communicated with described vent pipe (25) fluid from washing section (22) is set, to dilute the described concentrating urea aqueous solution that contains carbaminate and do not contain free ammonia substantially, the required urea concentration of acquisition in the aqueous solution.
18. as claim 16 or 17 described improving one's methods, it is characterized in that, described improve one's methods further comprising the steps of:
-set in advance pipeline (27) at described washing section (22) and described urea recovery zone (3), add described urea recovery zone (3) with the gas phase that will discharge from described washing section (22), contain carbonic acid gas and may contain ammonia.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP07002265.2 | 2007-02-02 | ||
| EP07002265A EP1953137A1 (en) | 2007-02-02 | 2007-02-02 | Process and plant for the production of an aqueous solution comprising urea |
| PCT/EP2008/000698 WO2008092647A1 (en) | 2007-02-02 | 2008-01-30 | Process and plant for the production of an aqueous solution comprising urea |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101627009A CN101627009A (en) | 2010-01-13 |
| CN101627009B true CN101627009B (en) | 2013-07-24 |
Family
ID=38123984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008800039127A Active CN101627009B (en) | 2007-02-02 | 2008-01-30 | Process and plant for the production of an aqueous solution comprising urea |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US9988345B2 (en) |
| EP (2) | EP1953137A1 (en) |
| CN (1) | CN101627009B (en) |
| AU (1) | AU2008209989A1 (en) |
| CA (1) | CA2675611C (en) |
| PL (1) | PL2114872T3 (en) |
| RU (1) | RU2457200C2 (en) |
| WO (1) | WO2008092647A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102806011A (en) * | 2011-06-03 | 2012-12-05 | 中国石油化工股份有限公司 | Method for preparing automobile urea liquid reducing agent |
| CN105585364B (en) * | 2016-02-04 | 2022-01-28 | 河南心连心化学工业集团股份有限公司 | Inferior urea recovery device and recovery method thereof |
| DE102018120720B4 (en) * | 2018-08-24 | 2022-06-23 | Biogastechnik Süd GmbH | Apparatus and method for neutralizing an ammonium sulfate solution |
| DE102019208859A1 (en) * | 2019-06-18 | 2020-12-24 | Skw Stickstoffwerke Piesteritz Gmbh | Process for the continuous production of pure urea solutions by utilizing process water |
| US11912649B2 (en) | 2019-12-30 | 2024-02-27 | Stamicarbon B.V. | Ammonia removal from urea finishing |
| CN113101682B (en) * | 2021-05-28 | 2023-03-24 | 新疆心连心能源化工有限公司 | Device for reducing evaporation of condensation compound and stabilizing urea production and treatment method |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2848493A (en) | 1955-06-27 | 1958-08-19 | Allied Chem | Process for synthesis of urea |
| US4001320A (en) * | 1966-04-22 | 1977-01-04 | Stamicarbon B.V. | Method for controlling the ammonia and CO2 ratios in a urea manufacturing process |
| EP0611753B1 (en) * | 1993-01-07 | 1999-10-27 | Urea Casale S.A. | Improved process for urea production involving a carbon dioxide stripping step |
| US6063350A (en) * | 1997-04-02 | 2000-05-16 | Clean Diesel Technologies, Inc. | Reducing nox emissions from an engine by temperature-controlled urea injection for selective catalytic reduction |
| NL1028497C2 (en) * | 2005-03-09 | 2006-09-12 | Dsm Ip Assets Bv | Process for the preparation of a urea-containing aqueous stream. |
| RU2289471C1 (en) * | 2005-10-21 | 2006-12-20 | Открытое Акционерное Общество "Научно-Исследовательский И Проектный Институт Карбамида И Продуктов Органического Синтеза" (Оао Ниик) | Method and the installation for preparation of the solution of carbamide |
-
2007
- 2007-02-02 EP EP07002265A patent/EP1953137A1/en not_active Withdrawn
-
2008
- 2008-01-30 CN CN2008800039127A patent/CN101627009B/en active Active
- 2008-01-30 CA CA2675611A patent/CA2675611C/en active Active
- 2008-01-30 RU RU2009132707/04A patent/RU2457200C2/en active
- 2008-01-30 PL PL08707397T patent/PL2114872T3/en unknown
- 2008-01-30 AU AU2008209989A patent/AU2008209989A1/en not_active Abandoned
- 2008-01-30 US US12/525,655 patent/US9988345B2/en active Active
- 2008-01-30 WO PCT/EP2008/000698 patent/WO2008092647A1/en active Application Filing
- 2008-01-30 EP EP08707397.9A patent/EP2114872B1/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| EP2114872A1 (en) | 2009-11-11 |
| CN101627009A (en) | 2010-01-13 |
| RU2457200C2 (en) | 2012-07-27 |
| EP2114872B1 (en) | 2014-10-08 |
| CA2675611C (en) | 2015-11-17 |
| US20100140543A1 (en) | 2010-06-10 |
| US9988345B2 (en) | 2018-06-05 |
| PL2114872T3 (en) | 2015-03-31 |
| CA2675611A1 (en) | 2008-08-07 |
| AU2008209989A1 (en) | 2008-08-07 |
| EP1953137A1 (en) | 2008-08-06 |
| WO2008092647A1 (en) | 2008-08-07 |
| RU2009132707A (en) | 2011-03-10 |
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